CN111848488B - Method for synthesizing 3-selenoindole derivative - Google Patents
Method for synthesizing 3-selenoindole derivative Download PDFInfo
- Publication number
- CN111848488B CN111848488B CN202010565034.0A CN202010565034A CN111848488B CN 111848488 B CN111848488 B CN 111848488B CN 202010565034 A CN202010565034 A CN 202010565034A CN 111848488 B CN111848488 B CN 111848488B
- Authority
- CN
- China
- Prior art keywords
- selenoindole
- derivative
- reaction
- formula
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing a 3-selenoindole derivative. Under the action of a nonmetal additive, a compound 2-styrylaniline derivative and organic diselenide are used as raw materials, and a series cyclization reaction is realized by a one-pot method, so that the 3-selenoindole derivative with diversified structures is synthesized. The method has the advantages of simple operation, high reaction selectivity, wide universality, environmental protection and avoidance of the use of metal reagents.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing a 3-selenoindole derivative.
Background
Indole derivatives are an important class of organic compounds, and are widely found in molecular frameworks of biological medicines, foods, cosmetics, dyes, materials, pesticides, and natural products. Among the numerous indole derivatives, however, 3-selenoindole has been receiving attention due to its various excellent biological and pharmacological activities. Therefore, the efficient synthesis method has great application value and wide application prospect.
Over the past few decades, various strategies have been developed for the synthesis of 3-selenoindoles. Direct selenization at the 3-position of existing indoles is mainly performed by a series of suitable selenization reagents, using either metallic or metal-free methods (angelw. Chem. Int.ed.,2015,54,5772-5776 chem. Commu.2018, 54,8781-8784 green. Chem.,2017,19, 5559-5563. However, many available indole derivatives are expensive or have a limited range of C-Se bond formation limiting the widespread use of this approach. Tandem cyclization/selenylation reactions utilizing 2-alkynylaniline derivatives have attracted more attention than direct indole selenylation (Synlett.2019, 30,207-212, adv.Synth.Catl.2018, 360,180-185, org.chem.Front.2017,4, 1322-1330. The advantage of this approach is that an efficient and versatile approach can be devised for simultaneously building the indole backbone and forming the C-Se bond. Reports of using 2-vinylaniline as a starting material are rare. This is probably due to the lower degree of unsaturation and weaker activity of 2-vinylaniline than 2-alkynylaniline derivatives. In 2012, the document (chem. Commun.2012,48, 10052-10054.) reported that the tandem reaction of 2- (dibromo (chloro) vinyl) -N-methylsulfonylaniline with diselenide produced the corresponding 3-selenoindole. The scheme is adoptedStill under strongly basic conditions by 2-alkynylaniline as key intermediate. The literature (J.Heterocyclic.chem.1992, 29, 899-904.) describes the tandem polymerization of 2-vinylaniline derivatives with an excess of N-phenylselenosuccinimide (2.4 equivalents) to give 3-selenoindoles. This method lacks substrate versatility and requires harsh conditions (dry methyl chloride, N) 2 Atmosphere and 48h reaction time).
The method for synthesizing the 3-selenoindole derivative has harsh conditions and complex process, and the raw materials such as functionalized amine, indoline and some complex catalysts are not widely available, the preparation method is complex and the cost is high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing a 3-selenoindole derivative.
The technical scheme adopted by the invention is as follows: a method for synthesizing a 3-selenoindole derivative, comprising the following steps: in the presence of an additive, reacting a compound 2-styrylaniline derivative shown in a formula (I) and organic diselenide shown in a formula (II) serving as raw materials in a solvent to obtain a compound 3-selenoindole derivative shown in a formula (III); the reaction formula is as follows:
wherein the additive is N-fluoro-diphenyl sulfonamide.
Preferably, the solvent is pyridine.
Preferably, the molar ratio of: the compound of formula (I)/compound of formula (II)/additive was 1.0/1.0/2.0.
Preferably, the reaction temperature for preparing the 3-selenoindole derivative is 80-120 ℃.
Preferably, the reaction temperature for preparing the 3-selenoindole derivative is 100-120 ℃.
Preferably, the reaction time for preparing the 3-selenoindole derivative is 4-6h.
The invention has the following beneficial effects: under the condition that air and moisture are insensitive, the 2-styrylaniline derivative and diselenide which are used as raw materials are efficiently synthesized into the target 3-selenoindole derivative through a one-pot method under the action of a non-metallic organic additive. Compared with the prior method, the method has the advantages that the reaction conditions and the substrate universality are obviously improved, which is difficult to realize by other methods. The invention has the following advantages and innovations:
(1) The raw materials (the compound of the formula (I) and the compound of the formula (II)) have wide sources and are easy to be purchased or prepared commercially;
(2) The reaction universality is good, the yield is high, most of the reaction yield is over 90 percent, and the atom economy is high;
(3) The reaction does not involve metal compounds, and meets the requirement of green chemical development;
(4) The method for preparing the 3-selenoindole derivative has the advantages of simple and convenient operation, strong reaction selectivity, high product yield, mild reaction conditions, insensitivity to air and water, short reaction time, simple and convenient preparation process and product separation and purification and strong flexibility.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
After the completion of the following reaction, saturated sodium bicarbonate was added to the reaction mixture, followed by extraction, drying, and column separation to obtain a product.
(E) -2-styrylaniline (1 a) and diphenyl diselenide (2 a) were used as substrates, and different reaction conditions were set for the reaction, as shown in Table 1.
Using NFSI as an additive and THF as a solvent, it was found that the isolated yield of product 3a was 30% when 1 equivalent of 2a was reacted with excess NFSI (2.0 equiv) in air (reaction 1). Testing of different solvents found that basic solvent (pyridine) was the best solvent, increasing the yield of 3a to 56% (reaction 11), other basic solvents NEt 3 And piperidine (reactions 12-13) are less effective. By using NFSI (N-fluoro-bisbenzenesulfonamide), m-CPBA (m-chloroperoxybenzoic acid), feCl 3 、Cu(OAc) 2 As an additive to carry out the reaction(reactions 1, 14-16), the comparison shows that NFSI as an additive can react normally, while other compounds as additives, substantially no product can be obtained. Attempts to further improve the efficiency of product formation by increasing the reaction temperature and shortening the reaction time were successful, yielding 3a in 87% yield (reactions 17-19). When the amount of the additive is reduced or decreased (reactions 20 and 21), the yield of 3a is decreased. Therefore, the best reaction conditions are to perform the reaction in pyridine with NFSI as an additive in air at 110 ℃ for 4h.
TABLE 1 reaction conditions and yields of the reactions in example 1
a The reaction conditions are 1a (0.2 mmol), 2a (0.2 mmol), additive (0.4 mmol), solvent (2.0 mL), sealed tube, air atmosphere, 90 ℃ and 24h; b the separation yield; c ND = no detected; d 70℃； e 110℃； f 4h； g NFSI(0.3mmol)； h NFSI(0.5mmol).
as shown in Table 2, diphenyl diselenide (2 a) was reacted with various 2-styrylaniline compounds (1) having different substituents under the following conditions: 1 (0.2 mmol), 2a (0.2 mmol), NFSI (0.4 mmol), pyridine (2.0 mL), sealed tube, air atmosphere, 110 ℃,4h.
The steric effect of the R1 substituent has a significant effect on the reaction. The products 3b-3d are obtained in 69-90% yields when ortho-, meta-or para-methyl substituents are present on the Ar1 ring, respectively, probably because of steric hindrance, with lower yields of 3 b. With p-tert-butyl or methoxy on the Ar1 ring, yields 3e and 3f at 92% and 94%, respectively. The Ar1 ring carries an electron-withdrawing group such as chloro (3 g-3 i), fluoro (3 j,3 k), trifluoromethyl (3 l), nitro (3 m) in relatively low yields of 60-87%. Naphthalene ring formation gave product 3n in 89% yield. But alkyl groups cannot react, such as benzyl (3 o) on vinyl. Thus, the yield of reaction substrates with electron donating substituents on the Ar1 ring is slightly higher than that of substrates with electron withdrawing substituents.
Substrates with electron-withdrawing substituents on the Ar2 ring yield higher (3 p-3 y) than substrates with electron-donating substituents. When the Ar2 ring is a pyridine ring, the reaction cannot be carried out (3 z).
As shown in Table 3, 2-styrylaniline compound (1) and different diselenides (2) were reacted under the reaction conditions of 1 (0.2 mmol), 2 (1.0 equiv.), NFSI (2.0 equiv.), pyridine (2.0 mL), a sealed tube, and an air atmosphere at 110 ℃ for 4 hours, and the yield was the isolation yield. A series of diaryl diselenides having different functional groups on the aromatic ring are reacted as reactants with (E) -2-styrylaniline to give the desired product in high yield. Diaryl diselenide with an electron withdrawing group (-NO 2, -F) reacted with 1a to give the corresponding product (3 ze3 zf) in relatively high yields of 92% and 88%, respectively, compared to the product with an electron donating group (o-CH 3, m-CH3, p-CH 3) (3 za-3 zd). Good yields were also obtained with R3 as naphthalene and thiophene rings (3zg, 3zh). In addition to arylseleno derivatives, methylseleno derivatives are also important as metabolites of human selenium. (E) -2-styrylaniline with an electron donating group or an electron withdrawing group is reacted with dimethyldiselenane to give the product (3 zi-3 zm) in moderate yield.
TABLE 2 yield of products from Diphenyl diselenide (2 a) with various 2-vinylanilines with different substituents
TABLE 3 yield of the product obtained by reacting styrylanilines with different diselenides
The reaction was scaled up to 1.17g (6 mmol) of substrate and 1.78g (85% yield) of product with no significant change.
(E) -2-styrylaniline (1 a): diphenyldiselenide: NFSI was reacted at a molar ratio of 2:1:4 to obtain 3a in 48% yield, and to produce 3% of 2-phenylindole (5 a) (formula 1), it is hypothesized that 2-phenylindole (5 a) may act as an intermediate; the reaction was carried out under the same conditions with a molar ratio of 1; reacting 2- (4-methyl styryl) aniline (1 d) with 2-phenyl indole (5 a), diphenyl diselenide and NFSI in one pot to obtain 3a and 3d with yields of 26% and 20%, respectively (formula 3); when PhSeF was used as the selenizing reagent, the selenization reaction of 2-phenylindole (5 a) was successfully formed to form 3a in 93% yield. This result indicates a possible mechanism for the formation of PhSeF during cyclization.
From the above experiments, the following possible reaction mechanisms are derived: the diphenyl diselenide reacts with NFSI to form the electrophile PhSeXI. I. Subsequently, the electrophile attacks the C = C double bond of 1a to form selenide II. Intramolecular attack of the amino group results in the opening of the three-membered ring to produce intermediate III. The participation of pyridine facilitates the elimination of protons and the removal of the selenium moiety, thus giving indole intermediate 5a, with the release of the selenium electrophile PhSeXI. Finally, electrophilic addition of I to indole 5a forms 3-selenoindole 3a.
The following examples are specific reaction sequences of partial reactions carried out using the present invention.
Example 1
The preparation of 2-phenyl-3- (phenylseleno) indole has the following structural formula:
under the air atmosphere, adding raw material 2-styryl aniline (0.2 mmol), diphenyl diselenide (0.2 mmol) and additive NFSI (0.4 mmol), pyridine (2 mL), reacting for 5h at 100 ℃, and separating the product by 86%.
1 H NMR(500MHz,CDCl 3 )δ8.50(s,1H),7.78-7.76(m,3H),7.50-7.43(m,4H),7.37-7.34(m,1H),7.31-7.27(m,3H),7.21-7.15(m,3H)； 13 C NMR(125MHz,CDCl 3 )δ142.0,136.1,134.0,132.0,131.9,129.0,128.5,128.5,128.3,125.4,123.2,121.0,120.8,111.0,95.8.
Example 2
The preparation of 2- (4-tert-butylphenyl) -3- (phenylseleno) indole, the structural formula is as follows:
under the air atmosphere, raw materials of 2- (4-tert-butylstyrene) aniline (0.2 mmol), diphenyl diselenide (0.2 mmol) and additives of NFSI (0.4 mmol) and pyridine (2 mL) are added to react for 6 hours at 120 ℃, and the separation yield of the product is 94%.
1 H NMR(400MHz,CDCl 3 )δ8.53(s,1H),7.71-7.69(m,3H),7.50-7.45(m,3H),7.32-7.28(m,1H),7.25-7.19(m,3H),7.18-7.12(m,3H),1.38(s,9H)； 13 C NMR(125MHz,CDCl 3 )δ151.7,142.1,136.1,134.2,132.2,129.1,129.0,128.2,128.1,125.6,125.3,123.1,121.0,120.8,110.9,95.3,34.7,31.2.
Example 3
The preparation of 2-naphthyl-3- (phenylseleno) indole has the following structural formula:
under the air atmosphere, adding raw material 2-naphthylvinylaniline (0.2 mmol), diphenyl diselenide (0.2 mmol) and additive NFSI (0.4 mmol), pyridine (2 mL), reacting at 120 ℃ for 5h, and separating the product with the yield of 95%.
1 H NMR(400MHz,CDCl 3 )δ8.59(s,1H),8.15(s,1H),7.88-7.82(m,4H),7.76(d,J＝8.0Hz,1H),7.54-7.51(m,2H),7.46(d,J＝8.0Hz,1H),7.35-7.29(m,3H),7.24(d,J＝7.2Hz,1H),7.19-7.13(m,3H)； 13 C NMR(125MHz,CDCl 3 )δ141.9,136.3,134.1,133.1,133.1,132.2,129.4,129.0,128.5,128.3,128.2,127.8,127.7,126.6,126.5,126.0,125.5,123.3,121.1,120.9,111.0,96.5.
Example 4
Preparation of 2- (4-methoxyphenyl) -3- (phenylseleno) indole, structural formula is as follows:
under the air atmosphere, adding raw materials of 2- (4-methoxystyryl) aniline (0.2 mmol), diphenyl diselenide (0.2 mmol), additives of NFSI (0.4 mmol) and pyridine (2 mL), and reacting for 4 hours at 100 ℃ to obtain the product with the separation yield of 92%.
1 H NMR(400MHz,CDCl 3 )δ8.58(s,1H),7.75-7.72(m,3H),7.49(d,J＝8.0Hz,1H),7.36-7.28(m,4H),7.24-7.17(m,3H),7.03(d,J＝8.8Hz,2H),3.90(s,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.9,142.2,136.0,134.2,132.2,129.8,129.0,128.2,125.4,124.5,122.9,121.0,120.6,114.1,110.8,95.0,55.3.
Example 5
The preparation of 2-phenyl-3- (phenylseleno) -6-methylindole has the following structural formula:
under the air atmosphere, adding raw materials of 2-styryl-5-methylaniline (0.2 mmol), diphenyl diselenide (0.2 mmol) and additives of NFSI (0.4 mmol), pyridine (2 mL), and reacting for 5h at 110 ℃, wherein the isolation yield of the product is 94%.
1 H NMR(400MHz,CDCl 3 )δ8.45(s,1H),7.73(d,J＝6.8Hz,2H),7.55(d,J＝8.4Hz,1H),7.46-7.36(m,3H),7.25-7.22(m,3H),7.16-7.08(m,3H),7.03(d,J＝8.0Hz,1H),2.51(s,3H)； 13 C NMR(125MHz,CDCl 3 )δ141.4,136.6,134.1,133.3,132.2,130.0,129.0,128.6,128.4,128.4,128.3,125.3,122.9,120.5,110.9,95.7,21.7.
Example 6
The preparation of 2-phenyl-3- (phenylseleno) -6-trifluoromethyl indole has the following structural formula:
under the air atmosphere, raw materials of 2-styryl-5-trifluoromethylaniline (0.2 mmol), diphenyl diselenide (0.2 mmol) and additives of NFSI (0.4 mmol) and pyridine (2 mL) are added to react for 6 hours at 110 ℃, and the isolation yield of the product is 87%.
1 H NMR(400MHz,CDCl 3 )δ8.77(s,1H),7.76-7.73(m,4H),7.50-7.42(m,4H),7.22-7.13(m,5H)； 13 C NMR(125MHz,CDCl 3 )δ144.6,135.1,134.5,133.4,131.3,129.2,129.2,128.8,128.6,128.5,125.8,125.3(d,J C-F ＝31.3Hz),125.0(d,J C-F ＝270Hz),121.3,117.8(q,J C-F ＝3.8Hz),108.6(q,J C-F ＝3.8Hz),96.4.
Example 7
The preparation of 2-phenyl-3- (4-nitrophenylseleno) indole has the following structural formula:
under the air atmosphere, adding raw materials of 2-styrylaniline (0.2 mmol), bis (4-nitrophenyl) diselenide (0.2 mmol) and additives of NFSI (0.4 mmol) and pyridine (2 mL), and reacting at 120 ℃ for 6h to obtain the product with the isolation yield of 89%.
1 H NMR(500MHz,CDCl 3 )δ8.75(s,1H),8.16(d,J＝8.5Hz,1H),7.95(d,J＝8.5Hz,2H),7.67(d,J＝7.0Hz,2H),7.62-7.56(m,1H),7.51(d,J＝8.5Hz,1H),7.47-7.40(m,3H),7.34-7.31(m,1H),7.28(d,J＝8.5Hz,1H),7.23-7.20(m,1H)； 13 C NMR(125MHz,CDCl 3 )δ145.8,145.3,142.8,136.2,133.2,131.5,131.4,129.0,128.8,128.4,127.8,124.5,123.9,123.7,121.6,120.4,111.3,94.1.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (6)
1. A method for synthesizing a 3-selenoindole derivative is characterized by comprising the following steps: in the presence of an additive, reacting a compound 2-styrylaniline derivative shown in a formula (I) and organic diselenide shown in a formula (II) serving as raw materials in a solvent to obtain a compound 3-selenoindole derivative shown in a formula (III); the reaction formula is as follows:
wherein the additive is N-fluoro-diphenyl sulfonamide;
the solvent is one of pyridine, THF, NMP and DMA.
2. A process for the synthesis of 3-selenoindole derivatives according to claim 1, characterized in that: the solvent is pyridine.
3. The method of synthesizing 3-selenoindole derivatives according to claim 1, characterized in that: calculated according to molar ratio: the compound of formula (I)/compound of formula (II)/additive was 1.0/1.0/2.0.
4. A process for the synthesis of 3-selenoindole derivatives according to claim 1, characterized in that: the reaction temperature for preparing the 3-selenoindole derivative is 80-120 ℃.
5. The method of synthesizing 3-selenoindole derivatives according to claim 4, wherein: the reaction temperature for preparing the 3-selenoindole derivative is 100-120 ℃.
6. A process for the synthesis of 3-selenoindole derivatives according to claim 1, characterized in that: the reaction time for preparing the 3-selenoindole derivative is 4-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010565034.0A CN111848488B (en) | 2020-06-19 | 2020-06-19 | Method for synthesizing 3-selenoindole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010565034.0A CN111848488B (en) | 2020-06-19 | 2020-06-19 | Method for synthesizing 3-selenoindole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111848488A CN111848488A (en) | 2020-10-30 |
| CN111848488B true CN111848488B (en) | 2022-12-27 |
Family
ID=72987647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010565034.0A Active CN111848488B (en) | 2020-06-19 | 2020-06-19 | Method for synthesizing 3-selenoindole derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111848488B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851566B (en) * | 2021-01-28 | 2022-04-12 | 苏州大学 | Synthesis method of alpha-oxo-selenoamide derivative |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987005A (en) * | 2016-10-26 | 2018-05-04 | 南通诺泰生物医药技术有限公司 | A kind of preparation method of 3- arylselenos benzazolyl compounds |
| CN107987004A (en) * | 2016-10-26 | 2018-05-04 | 南通诺泰生物医药技术有限公司 | (hetero) aryl indole base selenide compounds |
| CN108440375A (en) * | 2018-04-17 | 2018-08-24 | 浙江工业大学 | Using disulfide as the catalysis oxidation synthetic method of the 3- sulfydryl indole class compounds of sulphur source |
| CN108586311A (en) * | 2018-03-23 | 2018-09-28 | 温州医科大学 | A kind of preparation method of 3- thioethers indoles or 3- selenide indoles |
-
2020
- 2020-06-19 CN CN202010565034.0A patent/CN111848488B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987005A (en) * | 2016-10-26 | 2018-05-04 | 南通诺泰生物医药技术有限公司 | A kind of preparation method of 3- arylselenos benzazolyl compounds |
| CN107987004A (en) * | 2016-10-26 | 2018-05-04 | 南通诺泰生物医药技术有限公司 | (hetero) aryl indole base selenide compounds |
| CN108586311A (en) * | 2018-03-23 | 2018-09-28 | 温州医科大学 | A kind of preparation method of 3- thioethers indoles or 3- selenide indoles |
| CN108440375A (en) * | 2018-04-17 | 2018-08-24 | 浙江工业大学 | Using disulfide as the catalysis oxidation synthetic method of the 3- sulfydryl indole class compounds of sulphur source |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111848488A (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109053625B (en) | Preparation method of substituted benzothiazole C2 alkylated derivative | |
| CN110627693B (en) | Allyl sulfone compound and preparation method and application thereof | |
| CN111848488B (en) | Method for synthesizing 3-selenoindole derivative | |
| CN110256493B (en) | C2-phosphonoindole compound and preparation method thereof | |
| CN105669441A (en) | Preparation method of alpha-acyloxyketone compound | |
| CN111995554A (en) | Method for preparing asymmetric organic selenium ether compound by metal-free chemical oxidation method | |
| CN114213424B (en) | Synthesis method of furan [3,2-b ] pyridine derivative | |
| CN110511193A (en) | A kind of α -one thioamide analog compound and its synthetic method | |
| CN104774202A (en) | Synthesis method of 9H-pyridino[2,3-b]indole compounds | |
| FR2846325B1 (en) | NOVEL PROCESS FOR PREPARING A PESTICIDE SYNTHESIS INTERMEDIARY | |
| US9353130B2 (en) | Process for the in situ activation of zinc metal | |
| CN107417623B (en) | Method for synthesizing 5-diarylaminobenzimidazole derivative in one step | |
| CN110386903B (en) | Tetrazine-containing oligomeric phenylene acetylene compound and preparation method thereof | |
| CN107501024B (en) | Synthesis method of 1, 2-diiodo olefin compound | |
| CN107935913B (en) | Carbazole compound and synthesis method and application thereof | |
| CN112225685B (en) | 3-cyanoindole compound, preparation method and application thereof | |
| CN104140409A (en) | Efficient synthesis method of novel fluorescent material 1,3-dihydroisobenzofuran compound | |
| CN110590641B (en) | Green preparation method of 3-hydroxyisoindole-1-ketone series compounds | |
| Malmberg et al. | Conjugate additions with chiral lithium (2-pyridyl)-[(S)-2-(1-dimethylaminoethyl) phenyl] cuprate | |
| CN108689976B (en) | Method for synthesizing 4-iodo-tetrahydropyran derivative under catalysis of 5-sulfosalicylic acid and dichlorotitanocene | |
| CN111302914B (en) | Preparation method of beta-hydroxyethyl cinnamaldehyde | |
| CN111116496B (en) | Synthetic method of quinoxaline heterocyclic derivative | |
| CN112645886B (en) | Green production process of uracil | |
| CN113403635B (en) | Method for preparing N-substituted pyrrolidone derivative | |
| CN110452145B (en) | Synthetic method of alpha, beta-unsaturated selenium compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |